Synthesis of trichlorosilane from tetrachlorosilane and hydridosilanes

ABSTRACT

The invention relates to a process for the preparation of trichlorosilane (HSiCl3) which comprises the reaction of tetrachlorosilane (SiCU) with hydridosilanes in the presence of a catalyst.

STATE OF THE ART

Trichlorosilane is conventionally produced by treating powdered metallurgical grade silicon with blowing hydrogen chloride at 300° C.:

Si+3 HCl→HSiCl₃+H₂.

Yields of 80-90% can be achieved. It is an important intermediate in the production of solar silicon where the trichlorosilane is distilled in a complex process and decomposed on heated hyperpure silicon rods to silicon, silicon tetrachloride and hydrogen chloride:

2 HSiCl₃→Si+SiCld₄+2 HCl.

Trichlorosilane is also produced from silicon tetrachloride:

3 SiCl₄+Si+2 H₂→4 HSiCl₃ (+H₂SiCl₂+HCl)

at a temperature of T=500° C. (with a thermodynamically limited yield of 20%).

In the Bayer Process, SiCl₄ is reacted with activated carbon or activated carbon supported transition metals and barium as promotor at 1=600-900° C. with a SiCl₄/HSiCl₃ conversion rate ˜15%.

For the reaction of SiCl₄+H₂→HSiCl₃+HCl temperatures >1000° C. are required, the conversion rate is ˜20%, the energy consumption is ˜1.3 kWh/kg SiCl₄ conversion (http://www.gtsolar.com)

Non-industrial procedures are described e.g. in the following scientific documents:

a) Preparation of Trichlorosilane from Hydrogenation of Silicontetrachloride in Thermal Plasma: W. Qingyou, C. Hanbin, L. Yuliang, T. Xumei, H. Zhijun, S. Shuyong, Y. Yongxiang, D. Xiaoyan, In: Inorganic Materials 2010, 46 (3), 251-254. (Yield HSiCl₃ was ˜70% (max), average yield ˜60%, energy: ˜3.2 kWh/kg for HSiCl₃).

b) Gas-Dynamic and Thermal Process in the Synthesis of Trichlorosilane by Hydrogen Reduction of Silicon Tetrachloride in a High-Frequency Discharge: R. A. Kornev, V. A. Shaposhnikov, A. M. Kuz′min in: Russian Journal of Applied Chemistry 2014, 87 (9), 1246-1250.

c) Mechanism of the silicide-catalyzed hydrodehalogenation of silicon tetrachloride to trichlorosilane: H. Walter, G. Roewer, K. Bohmhammel, in: J. Chem. Soc. Faraday Trans. 1996, 92 (22), 4605-4608 (conversion rate ˜15%, T=600° C.).

d) Hydrodehalogenation of Chlorosilanes in the Presence of Metal Silicides: Experimental Studies of Gas and Solid Phase Composition related to Thermodynamic Calculations: K. Bohmhammel, G. Roewer, H. Walter. In: J. Chem. Soc. Faraday Trans. 1995, 91 (21), 3879-3882.

e) Catalytic conversion of silicon tetrachloride to trichlorosilane for a poly-Si process: J. Y. Lee, W. H. Lee, Y.-Ki Park, H. Y. Kim, N. Y. Kang, K. B. Yoon, W. C. Choi, O-Bong Yang, in: Solar Energy Materials and Solar cells 105 (2012) 142-147 (Use of carbon-based catalysts (metal-carbon composite catalyst in a continuous-flow fixed-bed reactor) T˜650° C., yield HSiCl₃ 8-20%).

f) Base-Catalyzed Hydrogenation of Chlorosilanes by Organotin Hydrides: U. Pätzold, G. Roewer in: Organosilicon Chemistry II, N. Auner, J. Weiss (editors), VCH 1996, 55-62; J. of Organomet. Chem. 1996, 508, 147-152 (SiCl₄+Bu₃SnH→HSiCl₃+SiH₄ (+H₂SiCl₂+H₃SiCl), where R₄PCl, and R₄NCl are suitable as catalysts to get the explosive SiH₄). However, tin hydrides are very toxic and not suitable for industrial use.

Patent publications related to the production of trichlorosilane include e.g. U.S. Pat. No. 7,442,824 B2, US2008/0112875 A1, US2013/0216464 A1, US2016/0002052 A1, US2017/0369325 A1.

Technical Problems

A preparatively facile conversion of SiCl₄ into HSiCl₃ in high yields is an economic necessity (B. Ceccaroli, O. Lohne, Handbook of photovoltaic Science and Engineering, Solar Grade Silicon Feedstock, Edited by A. Luque and S. Hegedus 2003, 167-172). Most desirable would be a selective monohydrogenation of SiCl₄ to give HSiCl₃, however, reduction of SiCl₄ with common reducing agents, e.g. LiH (W. Sundermeyer DE1080077B, 1957; W. Sundermeyer, L. M. Litz, Chemie-Ing.-Tech. 1965, 37, 14-18; H. J. Klockner, M. Eschwey, Chem.-Ing.-Tech. 1988, 60, 815-821) and LiAlH₄ (Hollemann-Wiberg, Handbuch der Anorganischen Chemie, 102. Auflage, Walter de Gruyter, Berlin, N.Y., 2007, S. 938), gives the perhydrogenated SiH₄ quantitatively lacking in any selectivity towards HSiCl₃.

In the conventional process of manufacturing HSiCl₃, silicon is reacted with gaseous HCl in a Direct Process in a fluidized bed reactor at 300-450° C. in large scale: Si+3 HCl→HSiCl₃ (80%)+SiCl₄ (20%)+H₂. A tremendous amount of SiCl₄ is formed which is recovered since the late 1970s according to: Si+3 SiCl₄₊₂ H₂→4 HSiCl₃ (T=500° C., yield 20%).

From the Direct Synthesis HSiCl₃ is contaminated with electronically active impurities such as chlorides of boron, phosphorous and arsenic along with traces of hydrocarbons. Performing the HSiCl₃ deposition to give silicon and HCl in the Siemens Process, only one third of silicon is converted to polysilicon, but one third is converted to SiCl₄ and one third is unconverted in the decomposition leaving the reactor exhaust gas which still contains HCl. The HSiCl₃ formation is dependent from silicon quality: technical grade silicon requires higher temperatures but produces more SiCl₄ simultaneously. Pure and highly pure silicon produces lesser amounts of SiCl₄ but increase overall costs drastically. At higher temperatures H₂SiCl₂ forms from disproportionation of HSiCl₃ (and gives SiCl₄!). Thus, silicon impurities catalyze SiCl₄ formation. Summarizing, technical processes to produce semiconductor silicon are based on CVD (chemical vapor deposition) of chlorosilanes or silanes. The process based on chlorosilanes have the common effect that only ca. 25% of the chlorosilane used is converted into the final silicon product, but 75% is converted into the by-product silicon tetrachloride (SiCl₄). As 75% of the world wide hyper pure silicon production is based on the Siemens Process using HSiCl₃ as starting material, it is the major factor for economics to profitably dispose SiCl₄, which mostly is converted to fumed silica (SiO₂) upon hydrolysis at high temperatures and thus reducing economic benefit (H. Jacob, Prax. Naturwiss. Chem. 1988, 37, 4; K. Bohmhammel, G. Roewer, H. Walter, J. Chem. Soc. Faraday trans. 1995, 91, 3879-3882). Until now intensive efforts to convert SiCl₄ into HSiCl₃ were concentrated on the development of processes of homogenous gas-phase hydrogenation at 1200° C. and of hydrogenation in the presence of metallurgical silicon at 600° C. Much work was investigated in the hydrodehalogenation of chlorosilanes in the presence of metal silicides (H. Walter, G. Roewer, K. Bohmhammel, J. Chem. Soc. Faraday Trans. 1996, 92, 4605-4608), but reaction temperatures for HSiCl₃ recovery were high (˜600° C.) and yields were low (conversion rates SiCl₄/HSiCl₃ 4-7 mol %). The technically preferred reaction 3 SiCl₄+Si+2 H₂→4 HSiCl₃ (+H₂SiCl₂+HCl) is performed at 500° C. with a thermodynamically limited yield of 20%. In the Bayer Process SiCl₄ is reacted with activated carbon or activated carbon supported transition metals and Ba (barium) as promotor at temperatures between 600° C. and 900° C. with a SiCl₄/HSiCI₃ conversion rate of ˜15%. For the reaction of SiCl₄+H₂→4 HSiCl₃+HCl temperatures >1000° C. are required, the conversion rate is ˜20%, the energy consumption is ˜1.3 kWh/kg SiCl₄ conversion (http://www.gtsolar.com).

Accordingly, there has been a strong demand for an economically viable process for selectively preparing trichlorosilane in high yields from easily available starting materials, which process is energy saving, proceeds at low temperatures, and which allows a simple separation of the trichlorosilane from by-products.

DESCRIPTION OF THE INVENTION

The present inventors discovered that trichlorosilane can be prepared in high yields from tetrachlorosilanes and hydridosilanes, which process is energy saving, proceeds at low temperatures, and allows a simple separation of the trichlorosilane from by-products.

In accordance with the present invention, a process for the preparation of trichlorosilane (HSiCl₃) is provided which comprises the reaction of tetrachlorosilane (SiCl₄) with hydridosilanes in the presence of a catalyst.

In a preferred embodiment of the present invention, the hydridosilanes are selected from the group consisting of the formulae:

R_(n)SiX_(m)H_(4-n-m)  (1), and

R_(o)Si₂X_(p)H_(6-o-p)  (2),

wherein

R is an organic group,

X is halogen or alkoxy,

n is 0 to 3, preferably 1 to 3, more preferably 2,

m is 0 to 2, preferably 0, and

n+m=0 to 3, preferably 1 to 3, more preferably 2,

o is 0 to 5, preferably 1 to 5,

p is 0 to 5, preferably 0, and

o+p=1 to 5.

In the above formulae (1) and (2), R is preferably selected from aromatic or aliphatic hydrocarbon groups preferably with up to 6 carbon atoms, preferably from C1 to C6 alkyl groups or C2 to C6 alkenyl groups, more preferably from C1 to C4 alkyl groups.

Organic of organyl groups R can be the same or different, and preferably R includes an aromatic group, such as phenyl, tolyl, and/or an aliphatic hydrocarbon group, more preferably R is an alkyl group, such as methyl, ethyl, n-, or iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, iso-pentyl, sec-pentyl, n-, iso- or sec-hexyl n-, iso- or sec-heptyl, n-, iso- or sec-octyl etc., even more preferably R is a n-alkyl group, or R is an alkenyl group.

More preferred groups R are selected from the group of Me=methyl, Et=ethyl, Vi=vinyl, n-Pr=n-propyl, i-Pr=iso-propyl, allyl, t-Bu=tert-butyl, n-Bu=n-butyl, Hex=n-hexyl, Ph=phenyl, p-Tol=para-tolyl, Bz=benzyl, and Mes=mesityl, or mixtures thereof. Most preferred R is a methyl group.

X is a halogen atom, preferably chlorine or bromine, more preferably chlorine or an alkoxy group such as C1 to C6 alkoxy, preferably methoxy or ethoxy.

Preferably the hydridosilanes are selected from the group consisting of SiH₄, H₃SiCl, H₂SiCl₂, MeSiH₃, Me₃SiH, Me₂SiH₂, Et₂SiH₂, MeSiHCl₂, Me₂SiHCl, PhSiH₃, Ph₂SiH₂, PhMeSiH₂, Pr₂SiH₂, Hex₂SiH₂, tBu₂SiH₂, Me₂Si(OEt)H, ViSiH₃, ViMeSiH₂, Me₂HSi—SiHMe₂, MeH₂Si—SiH₂Me, MeH₂Si—SiHMe₂, Me₃Si—SiHMe₂, Me₃Si—SiH₂Me, H₃Si—SiH₃, HSi₂Cl₅, preferably Me₂SiH₂.

The process according to the invention is carried out in the presence of a catalyst, which promotes the selective reduction of the SiCl₄ to HSiCl₃. The catalyst is preferably selected from the group consisting of:

-   -   R¹ ₄QZ, wherein R¹ is independently selected from hydrogen or an         organyl group (such as those described for R above), more         preferably an aromatic group or aliphatic hydrocarbon group,         even more preferably a n-alkyl group, and most preferably a         n-butyl group, Q is phosphorus, nitrogen, arsenic, antimony or         bismuth, and Z is halogen,     -   phosphines of the formula R¹ ₃P, wherein R¹ is as defined above,         preferably an organyl group (such as those described for R         above), preferably PPh₃ or n-Bu₃P,     -   amines of the formula R¹ ₃N, wherein R¹ is as defined above,         preferably an organyl group (such as those described for R         above), preferably n-Bu₃N or NPh₃,     -   N-heterocyclic amines, preferably non-N-substituted         methylimidazoles, such as 2-methylimidazole, and         4-methylimidazole,     -   an alkali metal halide, such as LiCl, and     -   an alkaline earth metal halide.

In a preferred embodiment of the invention the process for the preparation of trichlorosilane is carried out in the presence of a catalyst of the formula R¹ ₄QZ, wherein R¹ is an organyl group, more preferably an aliphatic hydrocarbon group, even more preferably a n-alkyl group, and most preferably a n-butyl group, Q is phosphorus or nitrogen, and Z is chlorine, Preferred catalysts are selected from the group consisting of:

-   -   quaternary ammonium or phosphonium compounds, such as         -   R¹ ₄PCl, wherein R¹ is hydrogen or an organyl group, which             can be the same or different, more preferably an aromatic             group or aliphatic hydrocarbon group, even more preferably a             n-alkyl group, and most preferably a n-butyl group, such as             n-Bu₄PCl,         -   R¹ ₄NCl, wherein R¹ is hydrogen or an organyl group, which             can be the same or different, more preferably an aromatic             group or aliphatic hydrocarbon group, even more preferably a             n-alkyl group, and most preferably a n-butyl group, such as             n-Bu₄NCl,     -   phosphines of the formula R¹ ₃P, wherein R¹ is hydrogen or an         organyl group, preferably an organyl group, preferably the         phosphine is PPh₃ or n-Bu₃P,     -   amines of the formula R¹ ₃N, wherein R¹ is as defined above,         preferably an organyl group, preferably the amine is n-Bu₃N or         NPh₃,     -   N-heterocyclic amines, preferably non-N-substituted         methylimidazoles, such as 2-methylimidazole, and         4-methylimidazole, preferred are N-heterocyclic amines with a         free nucleophilic electron pair at the nitrogen atom, which         means that the nucleophilicity at the nitrogen atom in such         N-heterocyclic amines is not reduced by inductive or mesomeric         interactions. In particular, cyclic amides are normally not         suitable as redistribution catalysts,     -   an alkali metal halide, such as NaCl, KCl, LiCl,     -   an alkaline earth metal halide, such as MgCl₂, CaCl₂).

Also a combination of two or more types of catalysts can be used.

Most preferred redistribution catalysts are selected from the compounds of the general formula R¹ ₄PCl, or R¹ ₄NCl, where R¹ is hydrogen or an organyl group and R¹ can be the same or different, preferably R¹ is an aromatic group such as R above, such as phenyl, tolyl, and/or an aliphatic hydrocarbon group, more preferably R is an alkyl group, such as methyl, ethyl, n-, or iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, tert-pentyl, neopentyl, iso-pentyl, sec-pentyl, n-, iso- or sec-hexyl n-, iso- or sec-heptyl, n-, iso- or sec-octyl etc., even more preferably R is a n-alkyl group, and most preferably the compound of the general formula R₄PCl or R₄NCl are n-Bu₄PCl or n-Bu₄NCl.

Further preferred catalysts are selected from triorganophosphines PR¹ ₃, R₁ is hydrogen or an organyl group such as R above and R¹ can be the same or different, more preferably R₁ is an alkyl such as described before, cycloalkyl or aryl group, most preferably the organophosphine is PPh₃ or n-Bu₃P. Further preferred catalysts are selected from triorganoamines NR¹ ₃, R₁ is preferably an organyl group, more preferably R is an alkyl group, and most preferably the triorganoamine is n-Bu₃N or NPh₃. Further preferred catalysts are N-heterocyclic amines such as non-N-substituted methylimidazoles such as 2-methylimidazole, and 4-methylimidazole, most preferably 2-methylimidazole.

Regarding the molar ratio of the catalyst in relation to the tetrachlorosilane it is preferably in the range of about 0.0001 mol-% to about 600 mol-%, more preferably about 0.01 mol-% to about 20 mol-%, even more preferably about 0.05 mol-% to about 2 mol-%, and most preferably about 0.05 mol-% to about 1 mol-%.

Herein, the molar ratio in % is defined as

[n (molar amount of the catalyst)/n (molar amount of the tetrachlorosilane)]×100. In another preferred embodiment according to the invention, the compounds of formula R¹ ₄PCl are formed in situ from compounds of the formulae R¹ ₃P and R¹Cl, wherein R¹ is H or an organyl group as defined above.

According to the invention, R¹ ₄PCl or R¹ ₄NCl can be also formed in situ, from R¹ ₃P or R¹ ₃N and R¹Cl by combination of the compounds in the reaction vessel in which the reaction is performed.

In the present invention, n-Bu₄PCl and n-Bu₄NCl was found to be a particularly effective catalyst.

In a particularly preferred embodiment, the present invention relates to a process for the preparation of trichlorosilane by reacting tetrachlorosilane with dimethylsilane.

In a particular preferred embodiment the present invention relates to a process for the preparation of trichlorosilane, which comprises the reaction of tetrachlorosilane with dimethylsilane according to the reaction equations (I) or (II):

Me₂SiH₂+2 SiCl₄→2 HSiCl₃+Me₂SiCl₂  (I),

Me₂SiH₂+SiCl₄→HSiCl₃+Me₂SiHCl  (II).

Accordingly, depending on whether the formation of Me₂SiCl₂ or Me₂SiHCl is preferred, which are intermediates in the manufacture of silicones and functionalized silicones, the molar ratio can be selected suitably. Also in this particular process the catalysts are preferably selected from R¹ ₄QZ, as defined above, wherein R¹ is an organyl group, more preferably an aliphatic hydrocarbon group, even more preferably a n-alkyl group, and most preferably a n-butyl group, Q is phosphorus or nitrogen, and Z is chlorine, and most preferably the catalyst is selected from n-Bu₄PCl and n-Bu₄NCl.

Another particularly preferred embodiment of the present invention relates to the process of reacting Me₃SiH+SiCl₄->Me₃SiCl+HSiCl₃.

The process for the preparation of trichlorosilane according to the invention, can be carried out in the presence or absence of a solvent. If a solvent is used the process of the present invention is carried out in the presence of one or more solvents, preferably selected from ether solvents. According to the present invention, the ether solvents can be selected from ether compounds, preferably selected from the group consisting of linear and cyclic aliphatic ether compounds. In the present invention, the term “ether compound” shall mean any organic compound containing an ether group —O—, in particular of formula R²—O—R³, wherein R² and R³ are independently selected from an organyl group R such as those mentioned above. Preferably, in the present invention in general R represents an organyl group, which is bound to the silicon atom via a carbon atom, and which organyl group can be the same or different. Preferably the organyl group is an optionally substituted, more preferably unsubstituted group, which is selected from the groups consisting of: alkyl, aryl, alkenyl, alkynyl, alkaryl, aralkyl, aralkenyl, aralkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloaralkyl, cycloaralkenyl, and cycloaralkynyl, even more preferably selected from alkyl, cycloalkyl, alkenyl and aryl, even further preferred selected from methyl, vinyl and phenyl, and most preferably R is a methyl group (herein abbreviated as Me).

Preferably, R² and R³ are substituted or unsubstituted linear or branched alkyl groups or aryl groups, which may have further heteroatoms such as oxygen, nitrogen, or sulfur. In the case of cyclic ether compounds, R² and R³ can constitute together an optionally substituted alkylene or arylene group, which may have further heteroatoms such as oxygen, nitrogen, or sulfur. The ether compounds can be symmetrical or asymmetrical with respect to the substituents at the ether group —O—. Also a mixture of one or more ether compounds and one or more non-ether compounds can be used as solvent. Preferably, the one or more non-ether compounds forming the mixture with one or more ether compounds are selected from solvents which are less polar than the ether compounds used, particular preferably from aliphatic or aromatic hydrocarbons. In a further preferred embodiment of the process according to the invention, the ether compounds used as solvents are selected from the group of linear, cyclic or complexing ether compounds. Herein, a linear ether compound is a compound containing an ether group R²—O—R³ as defined above, in which there is no connection between the R² and R³ group except the oxygen atom of the ether group, as for example in the symmetrical ethers Et₂O, n-Bu₂O, Ph₂O or diisoamyl ether (i-Pentyl₂O), in which R²=R³, or in unsymmetrical ethers as t-BuOMe (methyl t-butyl ether, MTBE) or PhOMe (methyl phenyl ether, anisol). A cyclic ether compound used as solvent is a compound in which one or more ether groups are included in a ring formed by a series of atoms, such as for instance tetrahydrofurane, tetrahydropyrane or 1,4-dioxane, which can be substituted e.g. by alkyl groups. In linear ether compounds, also more than one ether group may be included forming a di-, tri-, oligo- or polyether compound, wherein R² and R³ constitute organyl groups when they are terminal groups of the compounds, and alkylene or arylene groups when they are internal groups. Herein, a terminal group is defined as any group being linked to one oxygen atom which is part of an ether group, while an internal group is defined as any group linked to two oxygen atoms being a constituent of ether groups. Preferred examples of such compounds are dimethoxy ethane, glycol diethers (glymes), in particular diglyme or tetraglyme, without being limited thereto. In the sense of present invention, the term “complex ether” is understood as an ether compound as defined above which is capable of complexing cations, preferably metal cations, more preferably alkali and alkaline metal cations, even more preferably alkaline metal cations, and most preferably lithium cations. Preferred examples of such complex ethers according to the invention are glycol diethers (glymes), in particular diglyme, triglyme, tetraglyme or pentaglyme, or crown ethers, in particular 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, and diaza-18-crown-6 without being limited thereto. The ether solvent is preferably selected from the group consisting of linear ethers, such as diethyl ether, di-n-butyl ether, complexing ethers, such as dimethoxy ethane, diethylene glycol dimethyl ether (diglyme) or tetraethylene glycoldimethyl ether (tetraglyme), alkylated polyethylene glycols (alkylated PEGs), cyclic ethers such as dioxane, preferably 1,4-dioxane, 2-methyltetrahydrofurane, tetrahydrofurane, or tetrahydropyrane. In a particularly preferred embodiment of the process according to the invention, the ether compound is a high-boiling ether compound, preferably diglyme or tetraglyme. According to the present invention, the term “high-boiling ether compound” is defined as an ether compound according to above definition with a boiling point at 1.01325 bar (standard atmosphere pressure) of preferably at least about 70° C., more preferably at least about 85° C., even more preferably at least about 100° C., and most preferably at least about 120° C. High-boiling ethers can facilitate separation of the desired products from the reaction mixture containing the solvent and residual starting materials. The products in general have lower boiling points than the starting materials, and the boiling points of these products are also lower than the boiling point of high-boiling ethers of above definition. For instance, the respective boiling point (at standard atmosphere pressure) of HSiCl₃ is 32° C., while a representative higher-boiling ether compound diglyme has a boiling point of about 162° C. Application of higher-boiling ether compounds as solvents allows higher reaction temperatures to be utilized and simplifies separation of the desired products from the reaction mixture by distillation.

The process for the preparation of trichlorosilane according to the present invention is preferably carried out at a temperature in the range of about −40° C. to about 250° C., more preferably in the range of about 0° C. to about 200° C., still more preferably in the range of about 25° C. to about 150° C.

The process for the preparation of trichlorosilane according to the present invention is preferably carried out at a pressure from about 0.1 to about 10 bar, preferably the reaction is carried out at about normal pressure (about 1013 mbar).

The process of the present invention is preferably carried out under inert conditions. In accordance with the present invention, the term “inert conditions” means that the process is partially or completely carried out under the exclusion of surrounding air, in particular of moisture and oxygen. In order to exclude ambient air from the reaction mixture and the reaction products, closed reaction vessels, reduced pressure and/or inert gases, in particular nitrogen or argon, or combinations of such means may be used.

The process of the present invention can be carried out continuously or discontinuously, such as batchwise.

In a preferred embodiment of the process according to the invention, the resulting trichlorosilane and the chlorosilanes formed from the hydridosilanes are separated from the reaction mixture by distillation. The term “distillation” in the sense of the present invention relates to any process for separating components or substances from a liquid mixture by selective evaporation and condensation. Therein, distillation may result in practically complete separation, leading to the isolation of nearly pure components, or it may be a partial separation that increases the concentration of selected components of the mixture. The distillation processes, which may constitute separation step B), can be simple distillation, fractional distillation, vacuum distillation, short path distillation or any other kind of distillation known to the skilled person. The step of separating the trichlorosilane and the chlorosilanes formed from the hydridosilanes can comprise one or more batch distillation steps, or can comprise a continuous distillation process.

A particular preferred process of the present invention comprises further the steps of hydrogenating of the resulting chlorosilanes to hydridosilanes of the formulae (1) or (2), and recycling said hydridosilanes into the reaction with tetrachlorosilane.

For example in the particular process for the preparation of trichlorosilane, which comprises the reaction of tetrachlorosilane with dimethylsilane preferably according to the reaction equations (I) or (II):

Me₂SiH₂+2 SiCl₄→2 HSiCl₃+Me₂SiCl₂  (I),

Me₂SiH₂+SiCl₄→HSiCl₃+Me₂SiHCl  (II).

the resulting Me₂SiCl₂ or Me₂SiHCl are separated and at least a part thereof or all thereof are hydrogenated to Me₂SiH₂ which is used again in the reaction with tetrachlorosilane.

Preferably the step of hydrogenating the chlorosilanes is carried out with a hydrogenation agent selected from the group consisting of metal hydrides, preferably selected from the group of alkali metal hydrides, such as LiH, NaH, KH, alkaline earth metal hydrides, such as calcium hydride, or complex metal hydrides, such as LiAlH₄, NaBH₄, n-Bu₃SnH, (i-Bu₂AlH)₂ or sodium bis(2-methoxyethoxy)aluminum hydride, more preferably the hydrogenation agent is selected from LiAlH₄, LiH, CaH₂ or LiH which is formed in situ by admixture of LiCl and NaH and subsequent heating said mixture to a temperature in the range of about 60° C. to about 200° C.

Suitable hydrogenation agents generally include metal hydrides, therein preferably selected from binary metal hydrides, such as LiH, NaH, KH, CaH₂ or MgH₂, complex metal hydrides, such as LiAlH₄ or NaBH₄, and organometallic hydride reagents, such as n-Bu₃SnH, i-Bu₂AlH or sodium bis(2-methoxyethoxy) aluminum hydride, or a hydrogenation agent selected from boron-containing hydride donors, more preferably selected from organohydridoboranes, hydridoboranates, hydridoboronates and hydridoborates, even more preferably hydridoboranates, hydridoboronates and hydridoborates generated from the corresponding boranates, boronates and borates being the Lewis acid part of a frustrated Lewis acid/Lewis base pair and H₂. The use of tin hydrides is generally less preferred.

The most preferred hydrogenation agent is lithium hydride.

In a preferred embodiment of the process according to the invention, the amount of the hydrogenation agents, in particular of the metal hydride, preferably LiH in the hydrogenation reaction in relation to the chlorosilane compounds is in the range of about 1 mol-% to about 600 mol-%, preferably about 1 to about 400 mol-%, more preferably about 1 to about 200 mol-%, most preferably about 25 to about 150 mol-%, based on the total molar amount of the chlorine atoms present in chlorosilane compounds.

As described above the most preferred hydrogenation source is LiH, which is converted into lithium chloride (LiCl) in this reaction. In a particular preferred embodiment of such process using lithium hydride the LiCl formed is separated and subjected to the steps of purification, optionally mixing with KCl to prepare the LiCl—KCl eutectic composition, electrolysis of the eutectic or molten LiCl to obtain metallic Li and regeneration of LiH from the Li so prepared. It is the particular advantage of this embodiment that it renders the process of the present invention economical and efficient including in particular in the conversion reaction (Di→M2H), by recycling and valorizing the accruing LiCl and converting it back into LiH.

Therefore, the costs of the Li-metal appearing in both components (LiH and LiCl) is eliminated from the overall cost consideration and only the conversion costs involved in converting LiCl back into LiH is to be considered. In addition, the recycling is going along with the incumbent manufacturing route for LiH. In fact, the hydride material is made from LiCl in two sequential steps: a) electrolysis of the LiCl in the form of an eutectic system (with, e.g. KCl, Downs-Cell/Process) resulting in Li-metal; followed by step b) the hydrogenation of the Li-metal at elevated temperatures with hydrogen gas (H₂), which results into LiH (schematically):

(Complete stoichiometry:

2 LiCl→2 Li+Cl₂

2 Li+H₂→2 LiH).

The hydrogenation reaction is preferably carried out in the presence of one or more solvents, preferably selected from ether solvents such as those described above.

Accordingly, a particularly preferred embodiment of the present invention relates to a process for the preparation of trichlorosilane, which comprises

A) the reaction of tetrachlorosilane with dimethylsilane according to the reaction equation (I) or (II):

Me₂SiH₂+2 SiCl₄→2 HSiCl₃+Me₂SiCl₂  (I)

Me₂SiH₂+SiCl₄'HSiCl₃+Me₂SiHCl  (II),

in the presence of a catalyst of the formula R¹ ₄QZ, wherein R¹ is an organyl group, more preferably an aliphatic hydrocarbon group, even more preferably a n-alkyl group, and most preferably a n-butyl group, Q is phosphorus or nitrogen, and Z is chlorine,

B) separating the HSiCI₃ and Me₂SiCl₂ or Me₂SiHCl from the reaction mixture,

C) hydrogenating the Me₂SiCl₂ or Me₂SiHCl or part thereof with a hydrogenating agent which is selected from metal hydrides, preferably LiH, to form Me₂SiH₂, and

D) recycling the Me₂SiH₂, into step A).

The process of the present invention allows the preparation of trichlorosilane with high selectivity. In particular, the selectivity of the formation of HSiCl₃ defined as

Molar amount of HSiCl₃ formed/molar amounts of all hydrogenated silanes formed (ΣH₁₋₄SiCl₀₋₃, wherein the sum of number of hydrogen atoms and chlorine atoms adds up to 4)×100

is preferably at least 90%, preferably at least 95% and still more preferably at least 99%. That is, in accordance with the process of the present invention tetrachlorosilane is selectively reacted to trichlorosilane without the formation of higher hydrides such as H₂SiCl₂, H₃SiCl and H₄Si.

Also the conversion rates in the process of the present invention are preferably at least 90%, preferably at least 95% and still more preferably at least 99%. The term conversion rate in the present invention means that if for example Me₂SiH₂ is reacted and all hydrogen atoms are used to form HSiCl₃, the conversion rate is 100%. When also other monosilanes are formed (e.g., Me₂SiHCl), the conversion rate is accordingly reduced. The following examples are to illustrate:

Example 1) Me₂SiH₂+2 SiCl₄->Me₂SiCl₂+2 HSiCl₃ correspond to 100% conversion.

Example 2) 10 Me₂SiH₂+20 SiCl₄->5 Me₂SiCl₂+15 HSiCl₃+5 Me₂SiHCl+5 SiCl₄ (remaining) ->75% conversion rate (because 75% of all hydrogen atoms were used to form HSiCl₃, and 25% used for the formation of Me₂SiHCl).

Example 3) 10 Me₂SiH₂+20 SiCl₄->10 Me₂SiHCl+10 HSiCl₃+10 SiCl₄ (remaining) ->50% conversion rate since only half of all hydrogen atoms used were used to form HSiCl₃. Accordingly, for a 100% conversion rate, the hydridosilane used must be completely chlorinated to form HSiCl₃ and must not retain any of its hydrogen atoms. Accordingly, the conversion rate is defined by the formulas

(number of hydrogen atoms of the HSiCl₃ formed)/(total number of hydrogen atoms used of the hydridosilane used) or (number of hydrogen atoms of the hydridosilane used, which led to the formation of HSiCl₃)/(total number of hydrogen atoms of the hydridosilane used), or otherwise (for monosilanes R_(4-n)SiH_(n)) (molar amount of HSiCl₃ formed)/(molar amount of R_(4-n)SiH_(n) used)*n] (for disilanes one would have to adapt the formula accordingly). While usually conversion rates of 100% are desirable it is possible to operate at lower conversion rates to form e.g. Me₂SiHCl which can be used in the formation of functionalized polysiloxanes.

In the process for the preparation of trichlorosilane according to the invention preferably the molar ratios of the hydridosilanes to tetrachlorosilane (SiCl₄) are in the range of about 0.05 to about 2, preferably in the range of about 0.08 to about 1.5, even more preferably in the range of about 0.09 to about 1, most preferably about 0.1 to about 0.9.

In a preferred embodiment of the present invention in the process for the preparation of trichlorosilane the hydridosilanes are formed in situ from chlorosilanes and LiH. In a preferred embodiment of this in situ process SiCl₄ is reacted with LiH. It is assumed that in such process SiH₄ (in situ formed) reduces excess SiCl₄ to give HSiCl₃ selectively, whereas the monosilane formation from SiCl₄ and LiH (described by W. Sundermeyer, DE1 080077, 1957; W. Sundermeyer, L. M. Litz, Chem. Ing. Tech 1965, 37, 14-18; H. J. Klockner, M. Eschwey, Chem. Ing. Tech. 1988, 60, 815-821) gives the perhydrogenated silane lacking any selectivity.

It will be understood that any numerical range recited herein includes all sub-ranges within that range and any combination of the various endpoints of such ranges or sub-ranges, be it described in the examples or anywhere else in the specification.

It will be also understood that each number recited herein may be subject to a certain inaccuracy, so that each number should be associated with “about”.

It will also be understood herein that any of the components of the invention herein as they are described by any specific genus or species detailed in the examples section of the specification, can be used in one embodiment to define an alternative respective definition of any endpoint of a range elsewhere described in the specification with regard to that component, and can thus, in one non-limiting embodiment, be used to supplant such a range endpoint, elsewhere described.

It will be further understood that any compound, material or substance which is expressly or implicitly disclosed in the specification and/or recited in a claim as belonging to a group of structurally, compositionally and/or functionally related compounds, materials or substances includes individual representatives of the group and all combinations thereof.

While the above description contains many specifics, these specifics should not be construed as limitations on the scope of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art may envision many other possible variations that are within the scope and spirit of the invention as defined by the claims appended hereto.

EXAMPLES

The present invention is further illustrated by the following examples, without being limited thereto.

General

To obtain the organohydridosilanes as starting materials, the chlorosilanes, in particular, the organochlorosilanes R₃SiCl, R₂SiCl₂ and RSiCl₃ (R=alkyl, aryl, alkenyl) were converted in particular into their corresponding organomono-, di- and trihydridosilanes R₃SiH, R₂SiH₂ and RSiH₃ by hydrogenation (reduction) with conventional reduction agents, such as metal hydrides MH or MH₂, (M=alkali metal, earth alkali metal), or complex metal hydrides (LiAlH₄, NaBH₄, i-Bu₂AlH, etc.) or mixtures thereof in ethers as solvents (e.g. diethyl ether, di-n-butyl ether, diglyme, 1,4-dioxane or mixtures thereof). Because of safety and economic issues, the use of sodium hydride is preferred and attractive, but it reduces chlorosilanes only under drastic conditions, such as high temperatures that are around 250° C. [A. R. Gilbert, G. D. Cooper, R. W. Shade, Industrial and Engineering Chemistry 51, 5, 665-668, 1959]. On the other hand, lithium hydride (in diglyme as solvent) reduces chlorosilanes under moderate conditions in high yields [A. N. Kornev, V. V. Semenov, Organomet. Chem. in the USSR 4 (4), 420-422, 1991]. Considering the technically facile recycling of LiH from LiCl in KCl/LiCl melt, the use of lithium hydride is strongly favored for chlorosilane reductions.

Tetrachlorosilane, used as reaction partner for organosilanes to obtain trichlorosilane and organochlorosilanes, is the main byproduct of the Siemens Process including the trichlorosilane production from silicon metal and HCl, and is excessively available on the market. The reactions were performed mixing the reaction partners, i.e. the hydridosilanes (0.1 ml) and SiCl₄ in about 20-50 mol % excess required for the stoichiometric amount, dissolved in diglyme (0.2-0.3 ml) and the hydrogenation catalyst (1-3 w %) in an NMR tube. After cooling the sample with liquid nitrogen (about −196° C.), the tube was evacuated under vacuum (about 0.1 mbar), and sealed to avoid any losses of low boiling monosilanes such as Me₂SiHCl (b.p. 35° C.), MeSiHCl₂ (b.p. 41° C.), Me₂SiH₂ (b.p. −20° C.), MeSiH₃ (b.p. −58° C.), HSiCl₃ (b.p. 32° C.), H₂SiCl₂ (b.p. 8° C.), H₃SiCl (b.p. −30° C.) and SiH₄ (b.p. −112° C.). The boiling point of SiCl₄ is 57° C. The boiling point of Me₂SiCl₂ is 70° C. (all b.p. at normal pressure). NMR spectra were recorded depending on reaction time and temperature. For comparison of the catalyst activities each sample was first analyzed NMR-spectroscopically (²⁹Si— and ¹H NMR), either at r.t. after 8 hours or after 2 hours at 80° C. as reaction conditions. In case reduction of SiCl₄ was not completed further heating of the sample was accomplished (the experimental conditions for each experiment are depicted in Table 2). The molar ratios of products formed were determined by integration of relevant NMR signals that were assigned to specific products within the mixture; in case the organosilanes R₃SiH, R₂SiH₂ or RSiH₃ were completely consumed (quantitatively chlorinated), the conversion rate SiCl₄→HSiCl₃ is defined as 100%; if compounds R₂SiHCl are formed the maximum conversion rate is 50% accordingly.

After optimization and completion of the hydrogenation reaction SiCl₄+SiH→HSiCl₃+SiCl the NMR tube was opened to analyze the product mixture by GC-MS. Product identification was verified in all cases for the main products.

The amount of products formed can be estimated by the molar ratios as measured by NMR spectroscopy and the amount of starting material applied.

The optimum reaction conditions were evaluated from the NMR experiments and transferred onto the syntheses of HSiCl₃ from tetrachlorosilane with the organosilanes Me₂SiH₂, Me₃SiH and PhSiH₃ as hydrogen transfer reagents in preparative scale exemplarily. Even in preparative scale, the tetrachlorosilane reductions were performed in sealed glass ampoules at elevated temperature (80° C.) to avoid evaporation of compounds. NMR experiments as well as those in closed glass ampoules were run in high boiling solvents, such as diglyme, to reduce the overall pressure at elevated temperatures. Polar ethereal solvents are not required, nonpolar solvents (benzene) did not influence the course of reactions; tetrachlorosilane reductions to give HSiCl₃ also work in the absence of any solvent.

The glass ampoules had a length of 150 mm, outer diameter of 50 mm and a wall thickness of 2 mm (internal volume ˜200 ml). For high boiling organosilanes, such as PhSiH₃, reactions can be performed in open systems. This is exemplarily shown in the following section.

Identification of Compounds

Products were analyzed by ¹H and ²⁹Si NMR spectroscopy. The spectra were recorded on a Bruker AV-500 spectrometer equipped with a Prodigy BBO 500S1 probe. ¹H NMR spectra were calibrated to the residual solvent proton resonance ([D₆]benzene δH=7.16 ppm). Product identification was additionally supported by GC-MS analyses and verified identification of the main products. GC-MS analyses were measured with a Thermo Scientific Trace GC Ultra coupled with an ITQ 900MS mass spectrometer. The stationary phase (Machery-Nagel PERMABOND Silane) had a length of 50 m with an inner diameter of 0.32 mm. 1 μl of analyte solution was injected, 1/25 thereof was transferred onto the column with a flow rate of 1.7 ml/min carried by Helium gas. The temperature of the column was first kept at 50° C. for 10 minutes. Temperature was then elevated at a rate of 20° C./min up to 250° C. and held at that temperature for another 40 minutes. After exiting the column, substances were ionized with 70 eV and cationic fragments were measured within a range of 34-600 m/z (mass per charge). Product mixtures were diluted with benzene prior to the measurement.

²⁹Si NMR chemical shifts and coupling constants ¹J{²⁹Si—¹H} and ²J{²⁹Si—¹H} for the starting materials and reaction products formed are listed in Table 1. The spectroscopic and analytical data of starting hydridosilanes and products formed are consistent with published values. The monohydrogenations of tetrachlorosilane performed in sealed NMR tubes, the hydrogenation catalysts used, the SiCl₄→HSiCl₃ conversion rates and the molar product distributions are listed in Table 2.

TABLE 1 ²⁹Si NMR spectroscopic data of mono- and disilanes. δ ²⁹Si ¹J_(Si—H) ²J_(Si—H) Hydridosilane [ppm] [Hz] [Hz] MeSiH₃ −65.5 194.1 8.0 Me₂SiH₂ −38.1 187.6 7.5 Me₃SiH −16.6 182.9 7.0 Et₂SiH₂ −23.1 183.8 7.6 iPr₂SiH₂ −8.3 181.6 6.8 PhSiH₃ −60.2 200.0 6.4 Ph₂SiH₂ −33.9 198.2 6.0 PhMeSiH₂ −36.1 193.1 6.9 ViSiH₃ −64.5 198.6 — ViMeSiH₂ −40.5 192.7 — tBu₂SiH₂ 1.6 181.6 6.2 Hex₂SiH₂ −28.8 183.6 — Me₂Si(OEt)H 2.9 199.6 3.5 MeSiHCl₂ 10.9 280.1 7.8 Me₂SiHCl 11.0 223.1 7.2 Et₂SiHCl 18.5 216.9 8.0 iPr₂SiHCl 24.1 212.9 7.3 MeSiCl 12.8 — 8.6 Me₂SiCl₂ 32.5 — 7.6 Me₃SiCl 31.1 — 7.0 Et₂SiCl₂ 36.4 — — iPr₂SiCl₂ 38.2 — — PhSiCl₃ −0.4 — — Ph₂SiCl₂ 6.3 — — PhMeSiCl₂ 19.3 — 7.3 ViSiCl₃ −3.1 — — ViMeSiCl₂ 16.8 — — SiCl₄ −18.5 — — HSiCl₃ −9.1 372.6 — H₂SiCl₂ −11.4 292.1 — H₃SiCl −37.6 240.3 — SiH₄ −96.2 202.9 — EtOSiCl₃ −38.9 — — (EtO)₂SiCl₂ −56.3 — — (EtO)₃SiCl −70.3 — — MeH₂Si—SiH₂Me −67.8 185.8 3.6 Me₂HSi—SiHMe₂ −39.5 177.5 3.3 Me₂HSIA—SiBH₂Me −39.9/−66.7 180.9/180.5 — Me₃SiA—SiBHMe₂ −19.2/−39.4   —/172.5 — Me₃SiA—SiBH₂Me −18.3/−66.0 — — MeCl₂Si—SiCl₂Me 17.6 — — Me₂CISi—SiCIMe₂ 17.2 — —

TABLE 2 Selective conversion of SiCl₄ to HSiCl₃ with organohydridomonosilanes*⁾. catalyst conv. t/T Hydridosilane SiCl₄ entry Hydrido-silane (1-3 w %) rate¹⁾ (h/° C.) product distribution (mol %) (ml/mmol) (ml/mmol) a MeSiH₃ n-Bu₄PCl 100    2/80 HSiCl₃ (55), MeSiCl₃ (17), SiCl₄ (28) MeSiH₃ (0.04/0.54) 0.31/2.66 b Me₃SiH n-Bu₄PCl 100    2/80 HSiCl₃ (44), Me₃SiCl (45), SiCl₄ (11) Me₃SiH (0.10/0.86) 0.12/1.05 c Me₂SiH₂ n-Bu₄PCl 100    2/80 HSiCl₃ (55), Me₂SiCl₂ (27), SiCl₄ (18) Me₂SiH₂ (0.10/1.13) 0.35/3.06 d Me₂SiH₂ n-Bu₄PCl 78    8/r.t. HSiCl₃ (31), Me₂SiCl₂ (9), Me₂SiHCl (11), Me₂SiH₂ (0.05/0.57) 0.23/2.02 SiCl₄ (49) 100  +2/80 HSiCl₃ (40), Me₂SiCl₂ (19), SiCl₄ (41) e Me₂SiH₂ n-Bu₄NCl 66    8/r.t. HSiCl₃ (30), Me₂SiCl₂ (7), Me₂SiHCl (15), Me₂SiH₂ (0.05/0.57) 0.23/2.02 SiCl₄ (48) 100  +2/80 HSiCl₃ (42), Me₂SiCl₂ (20), SiCl₄ (38) f Me₂SiH₂ n-Bu₃P 52    8/r.t. HSiCl₃ (19), Me₂SiCl₂ (1), Me₂SiHCl (21), Me₂SiH₂ (0.05/0.57) 0.23/2.02 SiCl₄ (59) 100  +2/80 HSiCl₃ (32), Me₂SiCl₂ (13), Me₂SiHCl (8), SiCl₄ (47) g Me₂SiH₂ n-Bu₃N 41    8/r.t. HSiCl₃ (16), Me₂SiHCl (18), SiCl₄ (62), Me₂SiH₂ (0.05/0.57) 0.23/2.02 Me₂SiH₂ (4) 50  +2/80 HSiCl₃ (25), Me₂SiHCl (25), SiCl₄ (50) h Et₂SiH₂ n-Bu₄PCl 97    2/80 HSiCl₃ (50), Et₂SiCl₂ (24), Et₂SiHCl (1), Et₂SiH₂ (0.08/0.62) 0.21/1.86 SiCl₄ (30) 100 +24/80 HSiCl₃ (51), Et₂SiCl₂ (25), SiCl₄ (24) i Et₂SiH₂ n-Bu₄NCl 96    2/80 HSiCl₃ (52), Et₂SiCl₂ (24), Et₂SiHCl (2), Et₂SiH₂ (0.08/0.62) 0.21/1.86 SiCl₄ (27) 100 +24/80 HSiCl₃ (55), Et₂SiCl₂ (26), SiCl₄ (19) k Et₂SiH₂ n-Bu₃P 56    2/80 HSiCl₃ (31), Et₂SiCl₂ (3), Et₂SiHCl (22), Et₂SiH₂ (0.08/0.62) 0.21/1.86 SiCl₄ (45) 100 +24/80 HSiCl₃ (54), Et₂SiCl₂ (24), SiCl₄ (22) l Et₂SiH₂ n-Bu₃N 45    2/80 HSiCl₃ (25), Et₂SiHCl (24), SiCl₄ (49), Et₂SiH₂ (0.08/0.62) 0.21/1.86 Et₂SiH₂ (2) 54 +24/80 HSiCl₃ (30), Et₂SiCl₂ (2), Et₂SiHCl (24), SiCl₄ (44) m MeSiHCl₂ n-Bu₄PCl 100    2/80 HSiCl₃ (46), MeSiCl₃ (43), SiCl₄ (11) MeSiHCl₂ (0.10/0.97) 0.15/1.30 n Me₂SiHCl n-Bu₄PCl 100    2/80 HSiCl₃ (45), Me₂SiCl₂ (45), SiCl₄ (10) Me₂SiHCl (0.10/0.9) 0.13/1.13 o PhSiH₃ n-Bu₄PCl 100    2/80 HSiCl₃ (60), PhSiCl₃ (19), SiCl₄ (21) PhSiH₃ (0.05/0.41) 0.20/1.73 p Ph₂SiH₂ n-Bu₄PCl 100    2/80 HSiCl₃ (57), Ph₂SiCl₂ (26), SiCl₄ (17) Ph₂SiH₂ (0.10/0.54) 0.18/1.54 q PhMeSiH₂ n-Bu₄PCl 100    2/80 HSiCl₃ (58), PhMeSiCl₂ (27), SiCl₄ (15) PhMeSiH₂ (0.07/0.53) 0.17/1.43 r iPr₂SiH₂ n-Bu₄PCl 56    2/80 HSiCl₃ (34), iPr₂SiCl₂ (3), iPr₂SiHCl (22), iPr₂SiH₂ (0.10/0.63) 0.22/1.89 SiCl₄ (41) n-Bu₄PCl 100 +30/80 HSiCl₃ (50), iPr₂SiCl₂ (24), SiCl₄ (26) s²⁾ Hex₂SiH₂ n-Bu₄PCl none   30/80 no reaction Hex₂SiH₂ (0.13/0.58) 2.00/1.74 t³⁾ tBu₂SiH₂ n-Bu₄PCl 50  12/120 HSiCl₃ (24), tBu₂SiHCl (26), SiCl₄ (50) tBu₂SiH₂ (0.10/0.51) 0.17/1.46 u⁴⁾ Me₂Si(OEt)H n-Bu₄PCl 20    2/80 HSiCl₃ (21), Me₂SiCl₂ (51), SiCl₄ (1), Me₂Si(OEt)H 0.11/0.95 EtOSiCl₃ (8), (EtO)₂SiCl₂ (7), (EtO)₃SiCl (1), (0.10/0.73) X (11) v ViSiH₃ n-Bu₄PCl 100    2/80 HSiCl₃ (60), ViSiCl₃ (18), SiCl₄ (22) ViSiH₃ (0.05/0.57) 0.30/2.61 w ViMeSiH₂ n-Bu₄PCl 100    2/80 HSiCl₃ (60), ViMeSiCl₂ (29), SiCl₄ (21) ViMeSiH₂ (0.10/0.94) 0.26/2.30 x Et₂SiH₂ n-Bu₄PCl 93    2/80 HSiCl₃ (62), Et₂SiCl₂ (26), Et₂SiHCl (4), Et₂SiH₂ (0.10/0.77) 0.20/1.70 SiCl₄ (8) 100  +2/80 HSiCl₃ (64), Et₂SiCl₂ (31), SiCl₄ (5) *⁾General conditions: excess of SiCl₄ in addition to the stoichiometric amount is favored for full conversion: ~20-50 mol %. In case the SiCl₄ → HSiCl₃ conversion rate was not 100%, the sample was further heated for complete reduction (+ means: in addition to the aforementioned reaction conditions). ¹⁾The conversion rate SiCl₄ → HSiCl₃ is based on full chlorination of the starting organohydridosilane upon monohydrogenation of SiCl₄. In all cases, SiCl₄ is selectively monohydrogenated to give HSiCl₃. In cases of organohydridochlorosilane formation (e.g. R₂SiH₂ + SiCl₄ → HSiCl₃ + R₂SiHCl) the max. conversion rate SiCl₄ → HSiCl₃ is 50%. ²⁾Obviously due to the sterical demand of the hexyl groups, Hex₂SiH₂ does not react with SiCl₄ under the given conditions. ³⁾Obviously due to the sterical demand of the t-butyl groups, tBu₂SiH₂ reacts with SiCl₄ only at 120° C. to give selectively tBu₂SiHCl (SiCl₄ → HSiCl₃ conversion rate: 50%) ⁴⁾Excess SiCl₄ is nearly completely consumed by side reactions (ethoxychlorosilane formation). SiCl₄ remained in the reaction mixture in only 1%. X = not identified compounds.

As concluded from Table 2, the degree of monohydrogenation of tetrachlorosilane to selectively yielding trichlorosilane is mainly dominated by two factors: first by the steric demand of the organo-substituents at the silicon center of the monosilanes bearing hydrogen as transfer reagent and then by the hydrogenation activity of the catalysts investigated. Methyl-substituted hydridosilanes MeSiH₃, Me₂SiH₂ and Me₃SiH (entries a-g) start with the hydrogenation of SiCl₄ already at room temperature (˜25° C.) as listed for Me₂SiH₂ (entries d-g) showing SiCl₄/HSiCl₃ conversion rates between 40% and 80%, finally reacting quantitatively at 80° C. (100%). The experiments of entries d-g) clearly demonstrate a catalytic hydrogenation activity or potential decreasing in the series n-Bu₄PCl≈n-Bu₄NCl>n-Bu₃P>n-Bu₃N. This experimentally enables a facile reaction control to for example synthesize hydridochlorosilanes (R₂SiHCl) apart from trichlorosilane (entries e-g) at room temperature or, alternatively, to produce the fully chlorinated methylsilanes (entries a-c) under moderate conditions (2 h/80° C.). The experiments of series e-g clearly show the hydridosilane chlorination to happen stepwise. Noteworthy, in no experiment a double hydrogenation of SiCl₄ to yield dichlorosilane, H₂SiCl₂, was detected, the hydrodechlorination of tetrachlorosilane to give trichlorosilane is extraordinary selective. Comparable trends are recorded for diethylsilane, Et₂SiH₂ (entries h-I), already showing the increased steric demand of ethyl groups compared to the methyl-substituents: Even after 26 h reaction time at 80° C. reaction temperature Et₂SiHCl is nearly quantitatively formed under n-Bu₃N-catalysis (conversion rate SiCl₄/HSiCl₃ 54%, entry I) while Me₂SiHCl was formed from Me₂SiH₂ already after 2 h/80° C. (entry g). As expected, use of n-Bu₄NCl or n-Bu₄PCl as catalyst gave a conversion rate of 100% with full chlorination of the dihydridosilane (entries h and i). Considering the stepwise chlorination of methylsilanes (entries a, c, d) with tetrachlorosilane, it was expected that the methylchlorosilanes MeSiHCl₂ and Me₂SiHCl give trichlorosilane and the respective methylchlorosilanes quantitatively under n-Bu₄PCl catalysis—the experimental proof is depicted in the Table 2 (entries m and n). The steric demand of vinyl- and the planar phenyl-substituents at silicon is comparably low, the experiments showed no steric hindrance of the SiCl₄/HSiCl₃ transformation: The phenylsilanes (entries o-q) and vinylsilanes (entries v and w) were fully chlorinated by SiCl₄ to give conversion rates SiCl₄/HSiCl₃ of 100%. The increasing steric demand of isopropyl groups at silicon was convincingly demonstrated for iPr₂SiH₂ that gave a SiCl₄/HSiCl₃ conversion rate of 56% (2 h/80° C.) mainly giving iPr₂SiHCl as counterpart. Prolonged reaction time of 32 h yielded the Pr₂SiCl₂ quantitatively (entry r). The same counts for tBu₂SiH₂ that started to react only at 120° C. to give tBu₂SiHCl after 12 h quantitatively (SiCl₄/HSiCl₃ conversion rate 50%, entry t). Even more, Hex₂SiH₂ did not show any hydrogenation activity at all (entry s), it completely prevents SiCl₄/HSiCl₃ conversion. The very sensitive ethoxy-substituent of Me₂Si(OEt)H caused side reactions with excess tetrachlorosilane to give ethoxychlorosilanes (EtO)_(n)SiCl_(4-n) (n=1-3) as side products, but SiCl₄/HSiCl₃ conversion was 20% (entry u). The experiment of entry x demonstrates that excess SiCl₄ is not required for monohydrogenation to yield HSiCl₃ (conversion rates SiCl₄/HSiCl₃ 97% (entry h) vs 93% but increasing to 100% after 4 h/80° C. The main factor for product formation is determined by the stoichiometry of the reaction partners.

A) Synthesis of HSiCl₃ from Me₂SiH₂ and SiCl₄ in Preparative Scale

a) Synthesis of Me₂SiH₂ by reduction of Me₂SiCl₂ with LiH in THF

In a 250 ml three-necked flask equipped with a dropping funnel, reflux condenser and a magnetic stirrer were placed 7.22 g (0.88 mol, 97%) lithium hydride (LiH), suspended in 100 ml of thoroughly dried tetrahydrofurane (THF) under an inert nitrogen atmosphere. The THF/LiH suspension was carefully scaled from oxygen/air by degassing in vacuo and refilling with gaseous nitrogen to establish inert conditions. To the vigorously stirred suspension 56.84 g (53.6 ml, 0.44 mol) of dimethyldichlorosilane (Me₂SiCl₂) were slowly added over the dropping funnel. Upon addition, the reduction of Me₂SiCl₂ started after an induction period of 5 minutes with self-heating of the solution to about 54° C. Dimethylsilane (Me₂SiH₂, b.p.: −20° C.), formed continuously, evaporated and was frozen in a cooling trap (−196° C.) which was connected with the top of the reflux condenser. After Me₂SiCl₂ addition was completed (1 h, final temperature 50° C.), the mixture was subsequently heated to reflux (75° C. oil bath temperature) for an additional hour and then cooled down to r.t. To completely collect Me₂SiH₂ in the cooling trap, the reaction flask was applied to vacuum and the product was pumped off. Me₂SiH₂ inside the cooling trap was separated from THF by low temperature distillation and was isolated in 96% yield (25.4 g, 0.42 mol). Formed LiCl was isolated in 36.05 g (96% conversion of LiH into LiCl; theoretical yield after 100% conversion: 37.56 g) by removal of THF and remaining silanes in vacuo at 160° C., which is in line with the amount of formed Me₂SiH₂.

b) Synthesis of HSiCl₃

A glass ampoule (length: 15 cm, inner diameter: 5 cm, wall thickness: 2 mm) was evacuated in vacuo and subsequently filled with gaseous nitrogen to create an inert atmosphere. Then, 96.6 g (0.57 mol) SiCl₄, 2.15 g (0.007 mol, 2 w %) n-Bu₄PCl and 43 ml (39.63 g) diglyme were filled into the ampoule that was frozen at −196° C. (liquid N₂) and evacuated in vacuo. 13.58 g (0.23 mol) Me₂SiH₂ were added by low temperature condensation. Subsequently the ampoule was sealed, warmed to r.t. (25° C.) and heated to 80° C. for 5 h. After completion the reaction mixture was frozen (−196° C.) and the ampoule opened under an inert atmosphere. Volatile products were condensed into a flask that was connected to a Vigreux column (50 cm) and a distillery, which was connected to a cooling trap (−196° C.) to possibly collect unreacted Me₂SiH₂. The distillation condenser was cooled to 8° C. with a cryostat, the product receiving flask was cooled to −10° C. (HSiCl₃ b.p.: 32° C.) to reduce losses of HSiCl₃. Careful fractional distillation at normal pressure gave a first fraction containing 37 g of HSiCl₃ besides 6 g of SiCl₄ and 4 g of Me₂SiCl₂. The second fraction consisted of 22 g HSiCl₃, 15 g of SiCl₄ and 22 g of Me₂SiCl₂. 2 g of Me₂SiCl₂ remained in the residue. Me₂SiH₂ was completely consumed. After a second distillation step HSiCl₃ was isolated in an excellent isolated yield: 57 g (0.42 mol), 93% related to the molar amount of Me₂SiH₂ reacted.

B) Synthesis of HSiCI₃ from Me₃SiH and SiCl₄ in Preparative Scale

a) Synthesis of Me₃SiH by reduction of Me₃SiCl with LiH in Diglyme

As described for the synthesis of Me₂SiH₂, 34.00 g (0.31 mol) Me₃SiCl were reacted with 2.50 g LiH (0.31 mol). After completion of the chlorosilane reduction and collection of Me₃SiH together with some diglyme in the cooling trap, trimethylsilane was isolated by low temperature distillation in 97% yield (b.p. 6.7° C., 22.5 g, 0.30 mol). Formed LiCl was isolated in 12.94 g (97% conversion of LiH into LiCl; theoretical yield after 100% conversion: 13.26 g) by removal of diglyme and remaining silanes in vacuo at 160° C., which is in line with the amount of formed Me₃SiH.

b) Synthesis of HSiCl₃ In analogy to the HSiCl₃ synthesis with Me₂SiH₂ as hydrogenation agent, 12.34 g (0.17 mol) Me₃SiH, SiCl₄ (35.1 g, 0.21 mol), 0.5 g n-Bu₄PCl (1.7 mmol, 1.0 w %) and 20 ml diglyme were reacted in a sealed glass ampoule at 80° C. for 14 h. The ²⁹Si NMR analysis of the product mixture before work up showed full conversion of tetrachloro- into trichlorosilane (100%) with no remaining Me₃SiH. The molar ratio Me₃SiCl/HSiCl₃/SiCl₄ was 45/43/12. Careful fractional distillation (50 cm Vigreux column, distillation condenser: 8° C.) gave HSiCl₃ in 97% (21.78 g, 0.16 mol) related to the molar amount of Me₃SiH reacted. Boiling points: HSiCl₃ 32° C., Me₃SiCl 57° C.

C) Synthesis of HSiCl₃ from PhSiH₃ and SiCl₄ in preparative scale, open system The reaction of PhSiH₃ with SiCl₄ for the synthesis of HSiCl₃ was performed in an open system. In a two necked Schlenk-flask equipped with a reflux condenser (cooling temperature 27° C.) and a dropping funnel were admixed 72.19 g (424.9 mmol) SiCl₄, 52 ml diglyme and 0.54 g (1.8 mmol) n-Bu₄PCl under an inert N₂ atmosphere. The reaction mixture was heated to reflux (oil bath temperature 80° C.) and 9.50 g (87.8 mmol) of PhSiH₃ were slowly added via the dropping funnel. After addition was completed (30 min), the reaction mixture was heated to reflux (oil bath temperature 80° C.) for additional 4 hours. During the heating period HSiCl₃ continuously condensed in a cooling trap (−196° C.) that was connected with the reflux condenser. Subsequently, the product mixture was frozen (−196° C.), the reaction system evacuated and upon warming to room temperature all volatiles condensed into the cooling trap. After condensation was completed, all volatiles inside the cooling trap were condensed into a glass ampoule (−196° C., 59.44 g) with attached NMR tube. The glass ampoule was sealed in vacuo, warmed to r.t. and 0.5 ml of the product mixture were poured into the attached NMR tube. The NMR tube was disconnected from the glass ampoule and the condensed reaction products (Table 3) as well as the remaining residue within the reaction flask were investigated by ¹H and ²⁹Si NMR spectroscopy.

TABLE 3 Condensed product mixture (59.44 g) collected in the glass ampoule. compound mol % mmol g HSiCl₃ 60.3 246.1 33.34 H₂SiCl₂ 4.0 16.2 1.64 SiCl₄ 33.6 137.0 23.28 diglyme 2.1 8.8 1.18

PhSiH₃ was fully perchlorinated to give PhSiCl₃ that remained in the reaction flask. The corresponding conversion rate of SiCl₄→HSiCl₃/H₂SiCl₂ was 100%; the molar ratio of HSiCl₃/H₂SiCl₂ was 94/6.

D) Synthesis of HSiCI₃ and Me₂SiHCl in Preparative Scale

In analogy to the HSiCl₃ synthesis with Me₂SiH₂ as hydrogenation agent in B), 6.62 g (0.11 mol) Me₂SiH₂, SiCl₄ (38.12 g, 0.22 mol), 0.5 g n-Bu₃N (3.4 mmol, 1.4 w %) and 20 ml diglyme were reacted in a sealed glass ampoule with attached NMR tube at 80° C. for 4 h. After the sample was cooled to r.t., 0.5 ml of the product mixture was poured into the NMR tube, the NMR tube was sealed and products formed were analyzed NMR spectroscopically. The²⁹Si NMR analysis of the product mixture is depicted in Table 4 (yields in mol %).

TABLE 4 Hydrogenation of SiCl4 with Me2SiH2. silane 4 h/80° C. Me₂SiH₂ 2 Me₂SiHCl 34 SiCl₄ 34 HSiCl₃ 29 H₂SiCl₂ 1

The product mixture was subsequently heated for additional 2 hours at 80° C. to complete conversion of Me₂SiH₂ to Me₂SiHCl. Then the product mixture was frozen with liquid nitrogen (−196° C.), opened and all volatile compounds were pumped off into a cooling trap (−196° C.). Due to very similar boiling points of the targeted products HSiCl₃ and Me₂SiHCl (32° C. vs 35° C.), further separation was not possible with the distillation equipment available and therefore disregarded. The product distribution of the collected volatiles (35.4 g) was investigated by ¹H and ²⁹Si NMR analyses and is depicted in Table 5. Small amounts of SiCl₄ remained in the residue.

TABLE 5 Product distribution of the volatiles collected in the cooling trap. silane mol % mol g Me₂SiHCl 38 0.10 9.8 SiCl₄ 27 0.07 13.6 HSiCl₃ 35 0.10 12.0

The conversion rate SiCl₄/HSiCI₃ is 45%. Related to a quantitative reaction with a conversion rate of 50% the overall yield of product formation is 91%.

E) Synthesis of HSiCI₃ from Et₂SiH₂ and SiCl₄ Under LiCl and KCl Catalysis

0.08 ml (0.62 mmol) Et₂SiH₂, 0.17 ml SiCl₄ (1.45 mmol), 0.3 ml diglyme and 0.05 ml C₆D₆ were admixed together with catalytic amounts of lithium chloride or potassium chloride (0.10 mmol), respectively, in an NMR tube. The NMR tubes were cooled to −196° C., evacuated and sealed. The samples were heated and analyzed by NMR spectroscopy, according to Table 6.

TABLE 6 LiCl and KCl catalyzed reaction of Et₂SiH₂ and SiCl₄. LiCl catalysis KCl catalysis 80° C. 120° C. 120° C. 80° C. 120° C. 120° C. silane 4 h +18 h +36 h 4 h +18 h +36 h Et₂SiH₂ 29 8 — 31 31 28 Et₂SiHCl 3 20 28 — — 3 SiCl₄ 65 54 44 69 69 66 HSiCl₃ 3 20 28 — — 3 H₂SiCl₂ — <1 <<1 — — —

In case of the LiCl catalysis no Et₂SiH₂ remained after a reaction time of 54 h at 120° C. Et₂SiHCl was formed upon Et₂SiH₂ monochlorination selectively; the conversion rate SiCl₄→HSiCl₃ was 50% accordingly. Dichlorosilane formed only in traces.

Under comparable conditions HSiCl₃ and Et₂SiHCl formed only in 3% by replacement of LiCl against KCl, thus characterizing LiCl as the much more powerful hydrogenation catalyst; but the catalyst activity of LiCl is less compared to ammonium- and phosphonium chlorides and phosphines and amines.

F) Synthesis of HSiCI₃ from Methyihydridodisilanes and SiCl₄

F1) 0.1 ml (0.61 mmol) Me₂HSi—SiHMe₂, 0.21 ml SiCl₄ (1.8 mmol), 0.3 ml diglyme and 0.05 ml C₆D₆ were admixed with catalytic amounts of phosphonium chloride (0.02 mmol) in an NMR tube. The NMR tube was cooled to −196° C., evacuated and sealed. The sample was heated for 4 hours at 80° C. and analyzed by NMR spectroscopy (Table 7).

TABLE 7 Product distribution of the reaction of tetramethyldisilane with SiCl₄. silane mol % HSiCl₃ 52 (Me₂ClSi)₂ 24 SiCl₄ 24

This example clearly proves tetramethyldisilane as hydrogen shuttle to selectively monodehalogenate tetrachlorosilane to yield pure trichlorosilane (conversion rate SiCl₄/HSiCl₃: 100%). Organochlorodisilanes R_(n)Si₂Cl_(6-n) (n=1-5, R=organo-substituent) generally have much higher boiling points compared to the corresponding monosilanes. Thus, this process will strongly diminish the separation problems organochlorosilane/trichlorosilane by conventional distillation procedures. As the reaction conditions required for tetrachlorosilane monoreduction are comparably smooth, no disilane cleavage (for n=4-5) is performed with the hydrogenation catalyst—recycling of methylchlorodisilanes thus is preparatively facile by conventional reductions (in case of tetramethyldichlorosilane even LiH is suitable for the quantitative formation of the dihydridosubsituted disilane), making this process route very attractive for practical and industrial use.

F2 a) 0.05 ml (0.4 mmol) MeH₂Si—SiH₂Me, 0.4 ml SiCl₄ (3.5 mmol), 0.3 ml diglyme and 0.05 ml C₆D₆ were admixed with catalytic amounts of phosphonium chloride (0.02 mmol) in an NMR tube. The NMR tube was cooled to −196° C., evacuated and sealed. The sample was left at r.t. for 15 h and analyzed by NMR spectroscopy (Table 8).

TABLE 8 Product distribution of the reaction of dimethyldisilane with SiCl₄ at r.t. silane mol %* mol %** HSiCl₃ 37 68 SiCl₄ 46 — MeSiCl₃ 6 12 MeSiHCl₂ 7 13 MeSiH₂Cl 1 2 SiH₄ 1 2 Me₂Si₂Cl₄ 2 3 *including SiCl₄, **without SiCl₄

As concluded from Table 8 that contains the product distribution in mol % including both, excess SiCl₄ and without SiCl₄, HSiCl₃ was formed in 37% (68%) already at r.t. (15 h), while dimethyltetrachlorodisilane was formed in 2 mol %* (3 mol %)**. Thus, disilane cleavage under phosphonium chloride catalysis to yield MeSiCI₃ and MeSiHCl₂ is detectable already under smooth conditions. While SiH₄ is formed in 1 mol %* (2 mol %)**, notably, mono- and dichlorosilane was not formed at all. This proves the dimethyldisilane as hydrogen transfer reagent to reduce SiCl₄ with simultaneous disilane cleavage to yield MeSiCI₃ and MeSiHCl₂. From a comparable control experiment reacting an authentic sample of dimethyldisilane with catalytic amounts of n-Bu₄PCl at r.t. to 50° C., methylsilane MeSiH₃ (besides some oligosilanes) is formed quantitatively. This compound is not detected in the product mixture, but according to Table 2, entry a), methylsilane quantitatively reduces SiCl₄ to give HSiCl₃ and MeSiCI₃.

F2 b) A comparable sample to F2 b) [0.05 ml (0.4 mmol) MeH₂Si—SiH₂Me, 0.4 ml SiCl₄ (3.5 mmol), 0.3 ml diglyme, 0.05 ml C₆D₆ and catalytic amounts of phosphonium chloride (0.02 mmol)] was heated for 12 hours at 80° C. and the products formed analyzed by NMR spectroscopy (Table 9). The product distribution is listed in mol %, again, with excess SiCl₄ and without SiCl₄.

TABLE 9 Product distribution of the reaction of dimethyldisilane with SiCl₄ at 80° C. silane mol %* mol %** HSiCl₃ 38.7 69.5 SiCl₄ 44.4 — MeSiCl₃ 13.4 24.2 MeSiHCl₂ 3.5 6.3 *including SiCl₄, **without SiCl₄ Heating the sample at 80° C. for 12 h led to the formation of 39 mol %* (70 mol %)** HSiCl₃, 13 mol %* (24%)** MeSiCl₃ and 4 mol %* (6 mol %)** MeSiHCl₂. Notably, neither dimethyltetrachlorodisilane nor monosilane formation was detected.

F3) 0.07 ml of a methylhydridodisilane mixture (disilane distribution as depicted in Table 10), 0.21 ml SiCl₄ (1.8 mmol), 0.3 ml diglyme and 0.05 ml C₆D₆ were admixed together with catalytic amounts of phosphonium chloride (0.02 mmol) in an NMR tube. The NMR tube was cooled to −196° C., evacuated and sealed. The sample was heated for 4 hours at 80° C. and analyzed by NMR spectroscopy (Table 11).

TABLE 10 Disilane distribution of the starting disilane mixture. silane mol % (MeH₂Si)₂ 43 (Me₂HSi)₂ 31 MeH₂Si—SiHMe₂ 19 Me₃Si—SiHMe₂ 5 Me₃Si—SiH₂Me 2

TABLE 11 Product distribution of the reaction of a disilane mixture with SiCl₄. silane mol % HSiCl₃ 52 SiCl₄ 16 MeSiCl₃ 15 MeSiHCl₂ 6 (Me₂ClSi)₂ 4 H₂SiCl₂ 4 Me₂SiCl₂ 3

The experiment described under F3) unambiguously links together the Müller-Rochow-Direct

Process for methylchlorosilane production (Si+MeCI/Cu cat./350° C.→Me_(n)SiCl_(4-n) (n=1-3)) and the Siemens Process for silicon deposition. Considering the Direct Process Residue consisting of methylchlorodisilanes Me_(n)Si₂Cl_(6-n) (n=2-6) that needs to be recycled into valuable monosilanes under smooth reaction conditions for improving economic benefit and to reduce environmental pollution, it is suggested to (i) transfer the methylchlorodisilanes into their methylhydrido substituted congeners by conventional reduction routes (e.g. with LiAlH₄ with retention of the disilane skeleton or with LiH and simultaneous cleavage of highly chlorinated disilanes Me_(n)Si₂Cl_(6-n) (n<4) into the corresponding hydrido-substituted monosilanes and (i) the addition of excess SiCl₄ to the hydrido-(di)-silane mixture. Simultaneous disilane cleavage/SiCl₄ reduction and methylchlorosilane formation (as exemplarily depicted in Table 11) gives most valuable monosilanes in excellent yields, e.g. HSiCl₃ besides MeSiHCl₂.

All experiments performed and listed in Table 2 as well as the syntheses of trichlorosilane in preparative scales were run according to the stoichiometric requirements for a defined product formation. As mentioned earlier, the transformation of tetrachlorosilane into trichlorosilane occurred in an excellent selectivity regarding the monohydrogenation of SiCl₄ that was mostly used in a molar excess of 20-50% to prevent higher degrees of hydrogenation forming di- and/or monochlorosilanes. The SiCl₄ hydrogenation with Et₂SiH₂ (Table 2, entry x) clearly shows that the high molar excess of SiCl₄ is not necessary for HSiCl₃ formation. The excess used in our experiments was caused by safety requirements to prevent the principally possible formation of explosive monosilane, SiH₄, by full hydrogenation of tetrachlorosilane. The low boiling points of especially H₃SiCl (−30° C.) and SiH₄ (−112° C.) could have caused explosions of the glass ampoules or—even worse—the NMR tubes during measurements.

G) One Step Synthesis of HSiCl₃ from SiCl₄ Under n-Bu₄PCl Catalysis

Tetrachlorosilane (0.4 ml), diglyme (0.3 ml), C₆D₆ (0.05 ml) and n-Bu₄PCl (1 w %) were filled with a substoichiometric amount of lithium hydride (LiH, 4.3 mg) in an NMR tube under inert conditions. The reaction mixture was frozen (liquid N₂, −196° C.), evacuated and the NMR tube sealed in vacuo. After warming to r.t. the sample was heated to 100° C. for 10 h. The ²⁹Si NMR analysis proved selective formation of HSiCl₃ (conversion rate SiCl₄/HSiCl₃=100%). The molar ratio SiCl₄/HSiCl₃ was 85/15. Notably, formation of hydridosilanes H_(n)SiCl_(4-n) (n=2-4) could not been detected, but should have been expected. Monosilane formation from SiCl₄ and LiH (W. Sundermeyer, DE1080077, 1957; W. Sundermeyer, L. M. Litz, Chem. Ing. Tech 1965, 37, 14-18; H. J. Klockner, M. Eschwey, Chem. Ing. Tech. 1988, 60, 815-821) gives the perhydrogenated silane lacking any selectivity. Thus, in our case SiH₄ (in situ formed) reduces excess SiCl₄ to give HSiCl₃ selectively.

H) Synthesis of HSiCl₃ from SiCl₄ with Pentachlorodisilane (PCDS, HSi₂Cl₅) with Different Catalysts

Tetrachlorosilane (0.2 ml), pentachlorodisilane (0.2 ml), diglyme (0.2 ml) and C₆D₆ (0.05 ml) were admixed with different catalysts (0.02 mol) (as depicted in Table 12) in an NMR tube under inert conditions. The reaction mixtures were frozen (liquid N₂, −196° C.), evacuated and the NMR tubes sealed in vacuo. After letting the samples reach r.t. they were heated to 80° C. for 10 h. The results of the ²⁹Si NMR analyses are depicted in Table 12.

TABLE 12 Hydrogenation of SiCl₄ with PODS. SiCl₄/HSiCl₃ molar ratio silane catalyst conversion rate SiCl₄/HSiCl₃ PCDS n-Bu₄PCl 100% 65/35 n-Bu₃P 100% 63/37 n-Bu₃N 100% 65/35

In all experiments SiCl₄-monoreduction was selective with conversion rates SiCl₄/HSiCl₃ of 100%. Chlorination of PCDS should yield hexachlorodisilane (Si₂Cl₆) that is subsequently cleaved to give tetrachlorosilane, SiCl₄, by the catalysts used (C. J. Wilkins, J. Chem. Soc. 1953, 3409-3412; J. Inorg. Nucl. Chem. 1964, 26, 409-414; J. Tillmann, H.-W. Lerner, M. Wagner, DE102015105501A1, 2016) for reduction.

I) Synthesis of HSiCI₃ from SiCl₄ and Et₂SiH₂ in the Presence of nBu₄PCl and Benzene as Solvent

For a detailed study about the role of stoichiometry in the monoreduction of tetrachlorosilane a set of experiments was performed. Exemplarily, Et₂SiH₂ was reacted with SiCl₄ to give HSiCl₃ and Et₂SiCl₂ in C₆D₆ as solvent and under nBu₄PCl catalysis. According to the stoichiometry required for quantitative reactions, in experiment a) SiCl₄ and Et₂SiH₂ were reacted in a molar ratio of 2:1, in b) SiCl₄ was reacted in about 6 mol % excess and in experiment c) Et₂SiH₂ was used in 12 mol % excess for preparation of HSiCl₃. The experiments were performed in sealed NMR tubes and controlled NMR spectroscopically with increasing reaction temperatures and times. The results obtained are depicted in Table 12.

Preparation of a stock solution: 1.00 ml (7.7 mmol) Et₂SiH₂ were admixed with 1.80 ml (15.5 mmol) SiCl₄ and 2.8 ml benzene as solvent.

In the first of three competitive experiments, 0.6 ml of the stock solution and catalytic amounts of nBu₄PCl (5 wt %) were admixed in an NMR tube that was cooled to −196° C. The NMR tube was evacuated and sealed (exp. a). In the second experiment (analogously prepared to exp. a), 0.1 mmol of SiCl₄ (b) and in the third experiment 0.1 mmol of Et₂SiH₂ were additionally added. The three samples were heated to 80° C. and analyzed by NMR spectroscopy after 3, 6 and 30 h reaction time, respectively (Table 13).

TABLE 12 Selective conversion of SiCl₄ to HSiCl₃ with Et₂SiH₂ and benzene as solvent. a b (+SiCl₄) c (+Et₂SiH₂) 3 h, 6 h, 30 h, 3 h, 6 h, 30 h, 3 h, 6 h, 30 h, silane 80° C. 80° C. 80° C. 80° C. 80° C. 80° C. 80° C. 80° C. 80° C. HSiCl₃ 56.7 59.7 61.9 56.8 60.6 61.6 59.9 58.2 58.2 H₂SiCl₂ 3.0 5.8 6.0 2.8 4.1 4.2 8.5 10.0 9.1 Et₂SiCl₂ 18.3 24.0 25.9 18.9 23.8 25.1 26.7 27.6 28.5 Et₂SiHCl 9.2 2.5 — 6.9 1.4 — — — — SiCl₄ 12.9 8.1 6.2 14.6 10.1 9.1 4.9 4.2 4.2 ratio 95/5 91/9 91/9 95/5 94/6 94/6 88/12 85/15 86/14 HSiCl₃/ H₂SiCl₂

As expected, reacting equimolar amounts of Et₂SiH₂ and SiCl₄ (exp. a) the final molar ratio HSiCl₃/H₂SiCl₂ was 91/9 with still 6 mol % of SiCl₄ remaining. With excess SiCl₄ (exp. b) the final ratio HSiCl₃/H₂SiCl₂ was 94/6 and with excess hydridosilane the HSiCl₃/H₂SiCl₂ ratio was the lowest being 86/14. The series of experiments indeed prove that an increasing molar excess of SiCl₄ dominantly prevents double or even threefold hydrogenation and thus increases the SiCl₄→HSiCl₃ selectivity and conversion rates experimentally. Notably, comparable trends were formed running the experiments in diglyme as solvent.

J) Synthesis of HSiCI₃ from SiCl₄, Et₂SiH₂ and nBu₄PCl (without Solvent)

0.6 ml (5.2 mmol) SiCl₄ were admixed with 0.17 ml (1.3 mmol) Et₂SiH₂ and 0.05 g (0.17 mmol) nBu₄PCl in an NMR tube. The NMR tube was cooled to −196° C., evacuated and sealed. The sample was heated to 80° C. for 5 h and analyzed NMR spectroscopically. The product mixture consisted of 32.8% HSiCl₃, 45.9% SiCl₄, 11.7% Et₂SiCl₂, 9.3% Et₂SiHCl and 0.3% H₂SiCl₂. Further heating of the sample at 80° C. (additional 7 h) gave 42.0% HSiCl₃, 36.6% SiCl₄, 20.8% Et₂SiCl₂, and 0.6% H₂SiCl₂.

Advantages of the Invention

1) Products formed can be separated by distillation at normal pressure considering the boiling points:

HSiCl₃ b.p. 32° C., Me₂SiCl₂ b.p. 70° C., MeSiCl₃ b.p. 60° C., Me₃SiCl b.p. 57° C., Me₂SiHCl b.p. 35° C.

2) Reactants such as Me_(n)SiCl_(4-n) (n=1-3) and SiCl₄ are liquids that can be easily purified by conventional distillation—often SiCl₄ is already hyper pure from the Siemens Process—thus, HSiCl₃ obtained is highly pure. As HSiCl₃ quality in the technical process is strongly dependent from grain size and impurities, higher qualities are easily obtained from pre-cleaned starting materials.

3) SiCl₄/HSiCI₃ conversions conventionally worked at high temperatures (˜1000° C.) or under metal silicide catalysis (600° C.) and conversion rates of about 20% and 4-7%, respectively. The process claimed is by far energy saving (see Table 2, reactions at r.t.→80° C., some hours) and is characterized by extremely high conversion rates SiCl₄/HSiCl₃.

4) The “hydrogen shuttles” Me_(n)SiH_(4-n) (n=1-3) are easily available for silicon consuming companies running the Müller Rochow Direct Process (Si+MeCl (Cu cat., ΔT)→Me_(n)SiCl_(4-n), n=1-3; n=2: ˜90%). This is especially true for the main product Me₂SiCl₂.

5) Hydrogenation of Me_(n)SiCl₄, (n=1-3) is possible with all common reducing agents, such as alkaline and earth alkaline hydrides or complex metal hydrides, e.g. LiAlH₄ or NaBH₄. Most preferred is LiH, reductions are performed quantitatively (A. N. Kornev, V. V. Semenov, Metalloorg. Khim. 1991, 4, 860-863). LiCl formed by chlorosilane reductions is simply recycled in a LiCl/KCl melt electrolysis to give Li metal that is reacted with hydrogen gas at elevated temperatures to give LiH. Summarizing the Me₂SiCl₂→Me₂SiH₂→Me₂SiCl₂ cycle, Me₂SiH₂ is the hydrogen shuttle that is not consumed but easily recycled. LiH (or other reducing agents) are the “real” agents for monohydrogenation of SiCl₄→HSiCl₃, otherwise impossible to perform.

6) The stepwise chlorination of hydridosilanes RSiH₃ and R₂SiH₂, which is dependent from the reaction conditions and the hydrogenation catalysts used (see Table 2) allows the simultaneous formation of organochlorosilanes RSiHCl₂ and especially Me₂SiHCl. In no cases “triple” hydrogenation of SiCl₄ into H₃SiCl is observed; never the explosive SiH₄ formed (like e.g. in redistribution reactions of HSiCl₃ or hydrogenation of SiCl₄ with tin hydrides). Thus, a reaction

Me₂SiH₂+SiCl₄→Me₂SiHCl+HSiCl₃

is of high economic value. This process is highly economical and can be used in the silicone industry as well as for silicon deposition. As most of the silicon consuming companies are running both Direct Processes (Müller Rochow and Siemens) the process might be easily included into the major product streams. Additionally, all the included consumers are well equipped with highly developed distillation equipment to pre-purify the starting materials for production of highly pure products, e.g. HSiCl₃ and Me₂SiHCl. 

1. A process for the preparation of trichlorosilane (HSiCl₃) comprising reacting tetrachlorosilane (SiCl₄) with at least one hydridosilane in the presence of at least one catalyst.
 2. The process for the preparation of trichlorosilane (HSiCl₃) according to claim 1 wherein the at least one hydridosilane is selected from the group consisting of formulae: R_(n)SiX_(m)H_(4-n-m)  (1), and R_(o)Si₂X_(p)H_(6-o-p)  (2), wherein R is an organic group, X is halogen or alkoxy, n is 0 to 3, m is 0 to 2, and n+m=0 to 3, o is 0 to 5, p is 0 to 5, and o+p=1 to
 5. 3. The process according to claim 1, wherein R is chosen from aromatic or aliphatic hydrocarbon groups with up to 6 carbon atoms.
 4. The process of claim 1, wherein the hydridosilanes are selected from the group consisting of SiH₄, H₃SiCl, H₂SiCl₂, MeSiH₃, Me₃SiH, Me₂SiH₂, Et₂SiH₂, MeSiHCl₂, Me₂SiHCl, PhSiH₃, Ph₂SiH₂, PhMeSiH₂, iPr₂SiH₂, Hex₂SiH₂, tBu₂SiH₂, Me₂Si(OEt)H, ViSiH₃, ViMeSiH₂, Me₂HSi—SiHMe₂, MeH₂Si—SiH₂Me, MeH₂Si—SiHMe₂, Me₃Si—SiHMe₂, Me₃Si—SiH₂Me, and H₃Si—SiH₃.
 5. The process of claim 1, wherein the at least one catalyst is selected from the group consisting of: one or more compounds of the formula R¹ ₄QZ, wherein R¹ is independently chosen from hydrogen or an organyl group, Q is phosphorus, nitrogen, arsenic, antimony or bismuth, and Z is halogen, one or more phosphines of the formula R¹ ₃P, wherein R¹ is as defined above, one or more amines of the formula R¹ ₃N, wherein R¹ is as defined above, one or more N-heterocyclic amines, one or more alkali metal halides, and one or more an alkaline earth metal halides.
 6. The process of claim 1, comprising reacting tetrachlorosilane with dimethylsilane according to the reaction equations (I) or (II): Me₂SiH₂+2 SiCl₄→2 HSilC₃+Me₂SiCl₂  (I), Me₂SiH₂+SiCl₄→HSiCl₃+Me₂SiHCl  (II).
 7. The process according to claim 6, which is carried out in the presence of R¹ ₄QZ, wherein R¹ is an organyl group, Q is phosphorus or nitrogen, and Z is chlorine.
 8. The process according claim 1, which is carried out in the presence of at least one solvent.
 9. The process according to claim 1, which is carried out at a temperature in the range of about −40° C. to about 250° C.
 10. The process according to claim 1, which is carried out at a pressure from about 0.1 to about 10 bar.
 11. The process according to claim 1, which is carried out under inert conditions.
 12. The process according to claim 2, further comprising hydrogenating the resulting chlorosilanes to hydridosilanes of the formulae (1) or (2), and recycling said hydridosilanes into the reaction with tetrachlorosilane.
 13. The process according to claim 12, wherein the hydrogenating step is carried out with at least one hydrogenation agent selected from the group consisting of metal hydrides.
 14. The process according to claim 1, which comprises A) reacting tetrachlorosilane with dimethylsilane according to the reaction equation (I) or (II): Me₂SiH₂+2 SiCl₄→2 HSiCl₃+Me₂SiCl₂  (I) Me₂SiH₂+SiCl₄→HSiCl₃+Me₂SiHCl  (II),  in the presence of a catalyst of the formula R¹ ₄QZ, wherein R¹ is an organyl group, Q is phosphorus or nitrogen, and Z is chlorine, B) separating the HSiCl₃ and Me₂SiCl₂ or Me₂SiHCl from the reaction mixture, C) hydrogenating the Me₂SiCl₂ or Me₂SiHCl or part thereof (which means that not the entire amount of Me₂SiCl₂ or Me₂SiHCl is subjected to hydrogenating) with at least one metal hydride, to form Me₂SiH₂, D) recycling the Me₂SiH₂, into step A).
 15. The process according to claim 1, wherein the selectivity of the formation of HSiCl₃, defined as Molar amount of HSiCl₃ formed/molar amounts of all hydrogenated silanes formed (ΣH₁₋₄SiCl₀₋₃, wherein the sum of number of hydrogen atoms and chlorine atoms adds up to 4)×100 is at least about 90%.
 16. The process according to claim 1, wherein the molar ratios of the hydridosilanes to tetrachlorosilane (SiCl₄) is in the range of about 0.05 to about
 2. 17. The process according to claim 1, wherein the hydridosilanes are formed in situ from chlorosilanes and LiH.
 18. The process according to claim 1, which is carried out in the absence of at least one solvent.
 19. The process according to claim 12, wherein the hydrogenating step is carried out with at least one hydrogenation agent chosen from LiAlH₄, LiH, CaH₂ or LiH which is formed in situ by admixture of LiCl and NaH, and subsequently heating said mixture resulting from the admixture of LiCl and NaH to a temperature in the range of about 60° C. to about 200° C.
 20. The process according to claim 1, wherein R is chosen from a C1 to C6 alkyl group, and X is chlorine or bromine. 